Water-soluble high molal oxyalkylated esters, and method of making same



Patented Jan. 2, 1945 UNITED STATES PATENT OFFICE WATER-SOLUBLE HIGHMOLAL OXYALKYL- ATED ESTERS, AND METHOD OF MAKING SAME Melvin De Groote,University City, and Bernhard Keiser, Webster Groves, Mo., assignors toPetroiite Corporation, Ltd., Wilmington, Del., a

corporation of Delaware No Drawing. Original application July 7, 1941,Serial No. 401,376. Divided and this application March 9, 1943, SerialNo. 478,587 7 12 Claims.

This invention relates to a new chemical product, our presentapplication being a division of our pending application for patent, No.401,376,

filed July 7, 1941, for Process for breaking petroleum emulsions, whichsubsequently matured as U. S. Patent No. 2,324,488, dated July 20, 1943.One object of our invention is to provide a new chemical product orcompound that is particularly adapted for use as a demulsifier in theresolution of crude oil emulsions. Another object of our invention is toprovide a practicable method for manufacturing said new chemical productor compound.

Although one of the primary objects of our invention is to provide a newcompound or compo- OH (CaHZnO) mH in which m has its previoussignificance, and n represents a numeral varying from 2 to 4.

Thus, the bulk of the materials herein contemplated, articularly for useas demulsifiers, may be indicated within certain variations, ashereinafter stated, by the neutral ester derived by esterification ofone mole of a ycol of the kind sition of matter that is an efficientdemulsifier for crude oil emulsions of the water-in-oil type, the saidcompound or composition of matter may be employed in other arts, ashereinafter indicated.

The new chemical compound or composition of matter herein described, isexemplified by the. acidic, or preferably, neutral ester derived bycomplete estcrification of one mole of a polyal-- kylene lycol of thekind hereinafter described, with two moles of a fractional ester derivedfrom a hydroxylated material of the kind herein described, and apolybasic carboxy acid having not over six carbon atoms.

If a hydroxylated material, indicated for the sake of convenience by theformula T.OH, in which T is an alcoholic residue, is reacted with apolybaslc carboxy acid, which, similarly, may conveniently be of thedibasic type, and indicated by the formula HOOC.D.CO0H, in which D is adicarboxy acid residue, then the fractional ester obtained by reactionbetween equimolar quantities may be indicated by the following formula:

HOOC.D.COO.T

The polyethylene glycol may be characterized by materials Of the kindsuch as heptaethylene glycol, octaethylene glycol, nonaethylene glycol,decacthylene glycol, to and including heptadecaethylene glycol. Forconvenience these polyethylene glycols may be indicated by the followingformula in which m varies from '7 through 17.

Instead of polyethylene glycols, one may use polypropylene glycols, orpolybutylene glycols. Thus, for convenience, in the broadest aspect, thepolyalkylene glycols employed may be indicated by the following formula:

As indicated previously, the polybasic acids employed are limited to thetype having not more than six carbon atoms, for example, oxalic,

malonic, succlnic, glutaric, and adipic. Similarly, one may employ acidssuch as fumaric, maleic, glutaconic, and various others, includingcitric, malic, tartaric, and the like. The selection of the particulartribasic or dibasic acid employed is usually concerned largely withconvenience of manufacture of the finished ester, and also of the priceof the reactants. Generally speaking, the higher the temperatureemployed, the easier it is to obtain large yields of the esterifiedproduct. Although oxalic acid is comparatively cheap, it decomposessomewhat readily at slightly above the boiling point of water. For thisreason, it is more desirable to use an acid which is more resistant topyrolysis. Similarly, when a polybasic acid is available in the form ofan anhydride, such anhydride is apt to produce the ester with greaterease than the acid itself. For this reason maleic anhydride isparticularly adaptable: and also, everything else considered, the costis comparatively low on a per molar basis, even though somewhat higheron a per pound basis. Succinlc acid or the anhydride has many of theattractive qualities of maleic anhydride; and this is also true of.adipic acid. For purposes of brevity, the bulk of the compoundshereinafter illustrated will refer to the use of maleic anhydride,although it is understood that any other suitable polybasic acid may beemployed. Furthermore, for purposes of convenience, reference is made tothe use of polyethylene glycols. As has been previously indicated, suchslycols can be replaced by suitable polypropylene or polybutylenecompounds.

As far as the range of oxyalkylated compounds employed as reactants isconcerned, it is our preference to employ those having approximately8-12 oxyalkylene groups, particularly 8-12 oxyethylene groups. Ourpreference to use the oxyethylated compounds is due largely to the factthat they are commercially'available, and particularly so in twodesirable forms. The most desirable form is the so-called nonaethyleneglycol, which, although consisting largely of nonaethylene glycol, maycontain small amounts of heptaethylene and octaethylene glycols,'andpossibly minor percentages of the higher homologs. Such glycolsrepresent the upper range of distillable glycols; and they may beconveniently referred to as upper distillable ethylene glyco There is noparticularly good procedure for makings. sharper separation on acommercial scale; and it is understood that mixtures of One or more ofthe glycols may be employed, as well as a single glycol. As pointed out,it is particularly preferred to employ nonaethylene glycol ascommercially available, although it is understood that this productcontains other homologs, as indicated.

Substantially as desirable as the upper distilla- -ble polyethyleneglycols, are the lower non-distillable polyethylene glycols. Thesematerials are available in the form of a waxy water-soluble material,and the general range may vary somewhat from decato tetradecaethyleneglycol. As is well understood, the method of producing such glycolswould cause some higher homologs to be formed; and thus, even in thisinstance, there may be present some oxyethylene glycols within thehigher range above indicated. One need not point out that theseparticular compounds consist of mixtures, and that in some instances,particularly desirable esters are obtained by making mixtures of theliquid nonaethylene glycol with the soft, waxy, lower non-distillablepolyethylene glycols. For they sake of convenience, reference in theexamples will be to nonaethylene glycol; and calculations will be basedon a theoretical molecular weight of 414. Actually, in manufacture, themolecular weight of the glycol employed, whethera higher distillablepolyethylene glycol or a lower non-distillable polyethylene glycol, or amixture of the same, should be determined and reaction conducted on thebasis of such determination, particularly in conjunction with thehydroxyl or acetyl value.

It has been previously pointed out that it is immaterial how thecompounds herein contemplated are manufactured, although we have foundit most desirable to react the selected glycol or mixtures of glycolswith maleic anhydride in a ratio of two moles of the anhydride for onemole of the glycol. Under such circumstances, we have found littletendency to form longer chain polymers; and in fact, the product ofreaction, if conducted at reasonably low temperatures, appears to belargely monomeric. For convenience, such intermediate fractionalester'may then be considered as a dibasic or polybasic acid. One mole ofthe intermediate fractional ester so obtained is then reacted with twomoles of the alcoholic material of the kind subsequently described.

It is to be noted, however, that if one-prepares a fractional acidicester, then if two molesof the fractional acidic ester are reacted withone mole of the polyethylene glycol, there is no possibility for theformation of polymeric types of esteriflcation products under ordinaryconditions.

The hydroxylated compounds employed as reactants in one mode ofmanufactured the present compounds, are hydroxylatedracylated aminoethers containing:

I not over 60 carbon atoms; and

(b) An acyl radical derived from a detergent- "forming monocarboxy acidhaving at least 8 carbon atoms and not more than 32 carbonatoms, saidacylated aminoether being additionally characterized by the fact thatsaid aforementioned acyl radical is asubstituent for a hydrogen atom ofan alcoholic hydroxylradic'al.

Such hydroxyacylated aminoethers are obtained by reactions conducted insuch a manner as to introduce an acyl radical derived from a monocarboxydetergent-forming acid. Such acids are characterized by having at least8 and not more than 32 carbon atoms and are exempli- I fied by fattyacids, naphthenicacid, abietic acids, oxidized parafiin or wax acids, orthe like, or by simple modifications thereof which do not detract fromthe ability of the acid to combine with alkali to produce soap orsoap-like materials. As to' oxidized petroleum acids, see U. S. PatentNo. 2,242,837, dated May20, 1941, to Shields.

Thus, hydrogenated oleic acid, chlorinated naphthenic acid, orbrominated abietic acid will form such detergent-forming bodies with thesame ease as the parent materials themselves. The oxidized acidsobtained by blowing or oxidation of the acids or esters, aresatisfactory. Such acids have frequently been referred to collectivelyin the art as monocarboxy detergent-forming acids. Needless to say, theacylation need not be conducted by means of the acid itself, but may beconducted by means of any compound of the acid which contains the acidradical; for instance, an ester, an amide, an anhydride, an acylchloride, etc.

Common polyhydric alcohols include the glycols and glycerols. Thesepolyhydric alcohols are characterized by the ease with which two or moremolecules combine with elimination of water to form polyglycols,polyglycerols, or the like. These latter compounds are sometimesreferred to as ether alcohols, because the typical ether linkage,carbon-oxygen-carbon, appears at least once in such compounds. It isknown that certain hydroxyamines, particularly alkanolamines, containingalkanol radicals, .enter into the same kind of reaction with theformation of a hydroxylated aminoether. Possibly, the commonest exampleof analkanolaminegi'sian Jethanolamine, particularly diethanolamine andtri ethanolamine. It may be well to point out that one of the reactantsof intermediate products contemplated for the new composition, 'ofmatter ordemulsifying agentherein described, is derived from basiccompounds, 1." e., compounds in which the basicity approximates that ofthe parent hydroxyamine. Such basic amines are characterized by the factthat there is no aryl group directly attached to an amino nitrogengroup,

unless there be present at least one other amino radical capable ofcontributing a basic quality.

In other words, a hydrogen atom attached to an ing at least two carbonatoms and not more than 7 carbon atoms. Such acids include acetic acid,butyric acid, heptoic acid. etc. In the event that an amino nitrogenatom appears in which an aryl radical is directly attached to said aminonitrogen atom, as in the case of'phenyl diethanolamine, then thepresence of such non-basic amino nitrogen atom must be ignored and thecompound must contain at least one amino nitrogen atom of a basiccharacter elsewhere in the molecule. Other similar aryl alkanolamines,such as diphenyl ethanolamine, naphthyldlethanolamine,phenyldipropanolamine, etc. may be used. subject to the above-mentionedprovision.

In the following table of compounds, the letter T indicates an aminohydrogen atom, or any one of the substituents which have been suggestedas satisfactory to replace an amino hydrogen atom. The following tableis submitted purely by way of illustration, and indicates only a smallportion of the various materials which may be acylated with adetergent-forming monocarboxy acid to provide a component of thedemulsii'ying agents of the kind employed in the present- OHCzHaNCzHtOCIHAN OHCzHt CzH40H OHCzHa CIHIOH NCIHO C2H4N OHCaHc OHCrHi NC2H4OCzHaN OHCaHt T OHC2H4 T czHtoclHiN CiHlOH ClHtO 01H:

NCIHAOH clmo czflt CzHaO CaHt N T CzHtO czHt OHCzH OHCzH DEC 4 OECsHtOHCzHI OHOaHn C H OH In the above table, it is understood that where theradical CzHi occurs, it may be replaced by any other suitable radical,such as a CsHc, C4Ha radical, etc. Furthermore, it may be replaced by aresidue from a cyclohexyl radical, or a residue from a benzyl radical orthe like. Similarly, where the glycerol radical appears, a homolog maybe substituted instead, as, for example, betamethyl glycerol or thetetrahydroxyl derivative thereof. It is unnecessary to differentiatebe-- tween isomeric forms; and in some instances, one may have polymericforms containing a large number of residues derived from polyhydricalcohols or hydroxyamines, and of such a kind that there are presentperhaps20, 30, 40, or even 50 residues from the parent material ormaterials which contribute to the formation of the final molecule.Continuous etherization is considered as being polymerization, forpurposes of convenience. Such polymers may be considered a repetition ofthe monomer, taken any convenient number of times-for instance, two totwentythe manufacture of the composition of matter or demulsifler ischaracterized by having present at least one basic nitrogen atom, i. e.,a nitrogen atom unattached to any aryl radical and at least one hydroxylated hydrocarbon radical generally derived from an alkanolamine, orfrom a glycerylamine, such as monoglycerylamine, diglycer- I ylamine, ortriglycerylamine.

As to the manufacture of such intermediate compounds, which are used asreactants to produce the new composition of matter or demulsifiersherein contemplated, one need only point out that some of them are wellknown compositions of matter. Others can be produced, if desired, in thesame manner employed to produce those which are well known. One methodof producing such compounds is to heat the desired products undersuitable conditions, so as to cause dehydration to take place. Anothermethod is to treat the selected amine with a product such as an alkyleneoxide, including ethylene oxide, or with a product such as glycidol.Other methods involving dehydration in the presence of an acidic agent,for instance, dehydration of two moles of diethanolamine so as toproduce the ether type compound instead of morpholine, may be employed.It is possible that some of the types indicated above, like otherorganic compounds, are difiicult to prepare, but their derivatives canbe prepared more readily. In other words, since an acylated product isdesired, it is feasible, in some instances, to prepare the acylatedproduct by uniting a partially esterified polyhydric alcohol with apartially esterified alkanolamine, or by use of an equivalent method.This particular method of producing the desired type of chemicalcompound or intermediate reactant employed in the manufacture of our newcomposition of matter or new demulsifier, will be discussedsubsequently.

Attention is directed to U. S. Patent No. 2,393;- 494, to Melvin DeGroote and Bernhard Keiser, dated August 18, 1942. This particularpatent teaches a convenient method for making some of the compounds orintermediate reactants of the kind previously indicated. The said methodinvolves essentially the conversion of an ethanolamine or the like, suchas triethanolamine, into a monoor dialcoholate, and the reaction of thealcoholate with a halohydrin, such as glycerol chlorhydrin or glyceroldichlorhydrin. The alcoholates may be indicated by the followingformulae:

Such alcoholates react so as to liberate the alalkali metal halide, suchas sodium chloride or potassium chloride. Said patent illustrates, forexample, the manufacture of materials of the following type by means ofsuch reaction:

' OH olrnooim CSHAOH taken verbatim from said aforementioned patent:

"It has 'been previously pointed out that one may obtain acylatedderivatives of the amino ethers by use of the acylated alcoholatederived by utilitization of metallic sodium or potassium or the like. Insuch compounds the acyl radical is attached directly to the tertiaryamine residue or radical. However, if one employs an esterifiedchlorhydrin, i. e., the chlorhydrin derived from monoacetin,monostearin, monoabietin, mononaphthenin, or the like, one obtains achlorhydrin of the following type:

actants which include reactions of the following composition:

The above reactions can only be conducted in the absence of freealkali."

The following example for preparing a hydroxy aminoether is takenverbatim from said U. 8. Patent No. 2,293,494.

pounds of commercial triethanolamine containing 2 /2% monoethanolamineand 15% diethanolamine, are treated with pounds of a. 60% solution ofcaustic soda (1. e., 80 lbs. NaOH dissolved in 53 lbs. of water), so asto yield a pasty or semi-solid mass containing substantially no free orrelatively little free alkali. The wet mass is then reacted with extremecare, as previously noted, with commercial glycerol monochlorhydrin.After completion of reaction, the sodium chloride formed is separated byfiltration and hydraulic pressure. The final product represents acompound of technical purity and has the following composition;

N-CzH4OH OH olnlon in the hereto appended claims no reference is made tothe fact that the alcoholate is employed in substantial absence ofalkali, because it is deemed unnecessary to indicate that this conditionis the most desirable. The objection toan excess of alkali is thedestruction of the chlorhydrin and the formation of a polyhydric alcoholor the like, which appears in the completed product. Naturally, there isno objection to small amounts of excess alkali whose significance is notappreciable. It is to be noted in the claims that no reference is madeto separation of the alcoholate from water, excess alkali, unreactedamine, etc., whichmay be present, although, as previously indicated,such separatory procedure may be followed, if desired.

Having prepared a hydroxyaminoether of the kind previously described,the second step in the manufacture of the intermediate compound employedas a reactant is to acylate such product so as to introduce an acylradical derived from a detergent-forming monocarboxy acid. For purposesof convenience, such monocarboxy acid may be indicated by the formulaR'.COOH and the acyl group by R'.CO. It has already been indicated thatacylation may be conducted by use of the acid itself, or by use of anysuitable compound containing the acyl radical in labile form.

Attention is directed to U. S. Patents Nos. 2,154,422 and 2,154,423, toDe Groote, Keiser and Blair, both dated April 18, 1939. Both of saidpatents are concerned with products derived by esterification betweenintermediate amines containing an alcoholic hydroxy group and phthalicanhydride. It is necessary in the instances described in said patentsthat an alcoholic hydroxyl radical be present in reaction with phthalicanhydride. Insofar that the acylated aminoethers herein contemplated asreactants anolamine, dicyclohexyl ethanolamine, dicyclohexanolethylamine, benzyl diethanolamine, dibenzyl ethanolamine, benzyldipropanolamine,

tripentanolamine, trihexanolamine, ethyl hexyl.

ethanolamine, octadecyl diethanolamine, polyethanolamine, mono-, diandtri-glycerylamine,

for the manufacture of demulsifying agents must i be esterified withmaleic anhydride or the like, it is apparentthat an alcoholic hydroxylradical need be present, and that acyl radicals must be introduced sothat there is a residual hydroxyl radical attached either to ahydrocarbon radical, or to an acyl radical, such as a hydroxyl radicalwhich is part of a ricinoleyl radical. Furthermore, it is apparent thateven when acylation is accomplished with an acid having no hydroxylradicals, for instance, stearic acid, oleic acid, naphthenic acid, orthe like, then, in that event, one must acylate a hydroxy aminoetherhaving more than one free hydroxyl radical. A person skilled in the artwill readily understand how to employ the methods and compoundsdescribed in said two aforementioned patents to prepare acylatedderivatives from hydroxy aminoethers of the kind above described and theselected detergent-forming monocarboxy acid compound.

Said patents indicate the following amines which may be employed:Diethanolamine, mono dipropanolamine,

, acylated molecule of the other type.

etc.

Attention is also directed to the two aforementionedpatents to theextent that theydisclose and describe various glycerylamines and themethod of manufacturing the same. Such methods obviously are applicableto derivatives of the kind previously mentioned, such as beta methylglycerol, beta proply glycerol, beta ethyl glycerol, etc., as well asderivatives of the tetrahydroxyl compounds obtainable therefrom.

It has been previously pointed out that the chemical compounds employedas intermediates or as reactants for the production of the compositionof matter or new type of demulsifier herein contemplated, need notnecessarily be manufactured by first preparing the hydroyaminoether, andsubsequently acylating the same. As a matter of fact, in many instances,it is more convenient to acylate the desired polyhydric alcohol or thedesired hydroxyamine, and then combine the two acylated molecules oracylate one type of compound and combine with the un- Indeed, anexamination of what has been said previously and an examination of themethod suggested hereinafter, indicates that one can proceed to producea compound in which the acylated radical derived from thedetergent-forming radical is produced at whatever point is desired. Inother words, it may be introduced only in one or more hydroxyamineresidues which are present;

or the, acyl radical may be introduced only in one or more polyhydricalcohol residues which are present; or it may be introduced both intothe hydroxyamino residues which are present and into the polyhydricalcohol residue which is present. As previously pointed out, if desired,the acyl radical may be introduced more than once into the samehydroxyamino residue, or into the polyhydric alcohol residue, providedthere are available sufiicient alcoholic hydroxyl:

for such combination.

Acylation, of course, is identical with esterification for the purposesof the present description. In other words, instead ofreplacing thehydrogen atom of a hydroxyl group by an acyl radical, one can assumethat the complete hydroxyl radical hasbeen replaced by an oxyacylradical; i. e., a fattyacid radical; and thus, the product may bereferred to as esterified. Using such nomenclature, one can refer to analkanolamine as being partially esterified with a selecteddetergent-forming monocarboxy acid or a polyhydric alcohol asbeingpartially esteriified. The manufacture of partially esterified alcohols,such as superglycerinated fats, is well known; and such compounds haveconsiderable utility in the arts. Needless to say, the same methodemployed for producing superglycerinated fats may be employed inconnection with any polyhydric alcohol and may be employed in connectionwith other acids instead of fatty acids; for instance, the othernon-fatty detergent-forming monocarboxy acids, such as abietic acid,naphthenic acid, and the like. In view of this fact, no description isnecessary as to the method of preparing partially esterified polyhydricalcohols from detergentforming acids of the kind described. Furthermore,no description is necessary as to the method of 160 C. and 180 C. forabout two days.

preparing partially esterifled alkanolamines, in view of what has beensaid previously, and particularly in view of the complete description ofequivalent acylation procedure, which appears in the aforementionedUnited States Patents Nos. 2,154,422 and 2,154,423.

Reference is made to U. S. Patent No. 2,228,- 989, of Melvin De Groote,Bernhard Keiser and Charles M. Blair, Jr., dated January 14, 1941. Saidpatent describes compounds obtainable by a method which comprisesheating a partially esterified tertiary alkanolamine with a polyhydricalcohol to a temperature in excess of 100 C. for a period of timesufficient to cause condensation with elimination of water and theproduction of an ethereal reaction product. Although said patent isconcerned largely with derivatives of fatty acids, needless to say, thesame procedure may be applied to comparable compounds derived fromnaphthenic acid or abietic acid or the like. This is also true in regardto the preparation of subsequent Examples 4 10, inclusive. The followingthree examples appear in said patent.

"Example 1 (Example 1 of the patent) Commercial triethanolamine andcocoanut oil, in the proportions of 1 mole of cocoanut oil to 3 moles oftriethanolamine are heated to a temperature between about 160 C. and 180C. for about two hours. The resulting product consists mainly of themono-fatty acid ester of triethanolamine, with minor proportions of thedifatty acid ester, the tri-fatty acid ester, glycerin, etc. To thisreaction product is added somewhat more than 2 moles of glycerin, andthe resulting mixture is heated to a temperature between about Ifdesired, a current of dry nitrogen or other inert gas may be passedthrough to speed up the reaction. Condensation occurs between the fattyacid ester of the triethanolamine, and the glycerin, with the productionof ethereal reaction products, such as the dihydroxypropyl ether of themono-fatty acid ester of triethanolamine and other more complex etherealreaction products."

Example 2 (Example) of the patent) Trig1ycerylamine (tri di hydroxypropyl amine) and castor oil are reacted in the proportions of 3 molesof castor oil to 2 moles of triglycerylamine, with the production of aproduct consisting predominantly of the di-ricinoleic acid ester of thetriglycerylamine. The resulting mixture is further heated for a periodof about two days, with condensation between the glycerin andthediricinoleicacid ester of the triglycerylamine, and the production ofcorresponding ethereal condensation products."

Example 3 (Example 3 of the patent) Blown rapeseed oil anddiethanolethylamine, in the molecular proportions of 3 moles of theamine to 1 mole of the oil are heated together to a temperature betweenabout 150 C. and 180 C. for about two hours, with the production of areaction product containing a large proportion of the monoester of thediethanolethylamine, together with unreacted starting material,glycerin, etc. Something in excess of two moles of glycerin are added tothe reaction mixture, and the resulting product is heated to about 150C. to 180 C. for about two days, with the production of etherealreaction products of glycerin and the monoester of thediethanolethylamine."

similarly, attention is called to the U, 8. Patent No. 2,228,987, ofMelvin De Groote, Bernhard Keiser and Charles M. Blair, Jr., datedJanuary 14, 1941. Said patent describes compounds of the kind obtainableby a, method which comprises heating the triglyceride, a tertiaryalkanolamine having more than one alcoholic hydroxyl radical, and apolyhydric alcohol, to a temperature in excess of C. for a period oftime sufllcient to cause alcoholysis of a triglyceride and condensationbetween the resulting partially esterified alkanolamine, and partiallyesterified glycerine. The following examples appear in said patent:

"Example 4 (Examplei of the patent) Commercial triethanolamine, cocoanutoil and glycerin in the proportions of one mole of cocoanut oil to threemoles of triethanolamine and at least onemole of glycerin are heated toa temperature of between about and C. for a period of about fifty hours.If desired, a current of dry nitrogen may be passed through the reactionmixture. The resulting product contains a substantial and preponderatingamount of the ether resulting from the condensation of the mono-fattacid ester of triethanolamine and the monoand di-fatty acid ester ofglycerin, shown in the following formula:

N-CzHr-O-CHr-CzHKOH) (0 o o R) of which R represents the long carbonlinked chain of the cocoanut oil fatty acids.

Example 5 (Example 2 of the patent) Triglycerylamine (tri dihydroxy p ro p y lamine) and castor oil are reacted in the proportions of threemoles of castor oil to two moles of triglycerylamine, for aperiod ofabout two hours at a temperature of around 150 to 180 C. To the productso produced, which consists predominantly of the di-ricinoleic acidester of the triglycerylamine, is added about 50% of the monoricinoleicacid ester of glycerin, and the resuiting mixture is heated to about 150to 180 C. for about two days, with the production of mixed ethers of thedi-ricinoleic acid ester of triglycerylamine and the monoricinoleic acidester of glycerin, of the type formula:

in which two of the M's represent the acyl group corresponding toricinolefc acid and the other three represent hydrogen, and in which Rrepresents the carbon linked chain characteristic of ricinoleic acid.

"Example 6 (Example 3 of the patent) "Example 7 (Example 4 of thepatent) CHIC O O C2114 together with more complex ethereal derivativesof the amine and the monoglyceride.

"Example 8 (Example of the patent) "Commercial triethanolamine, a fattyoil and ethylene glycol in the molecular proportions of two moles of theamine to one mole of the oil to one mole of the ethylene glycol areheated to a temperature between about 150 and 180 C. for about two dayswith the production of a reaction product containing substantial amountsof the ether of the mono-ester of triethanolamine with the correspondingmono-glyceride and the ether of the mono-ester of triethanolamine withthe mono ester of ethylene glycol."

Furthermore, reference is made to U. S. Patent No. 2,228,988, of MelvinDe Groote, Bernhard Keiser and Charles M. Blair, Jr., dated January 14,1941, which describes compounds obtainable by a method which comprisesheating a partially esterified tertiary alkanolamine with a tertiaryalkanolamine at a temperature to an excess of 100 C. for a period oftime sufficient to effect condensation with the production of anethereal reaction product. Thefollowing examples are taken from saidpatent.

"Example 9 (Example 1 of the patent) of water from two molecules of themono-fatty acid ester of triethanolamine, with minor proportions of morecomplex ethers, ethers of the difatty acid ester of triethanolamine,ethers of the fatty acid esters of triethanolamine with glycerin ormonoor di-glycerides, etc.

Example 10 (Example 2 of the patent) The diricinoleic acid ester oftriglycerylamine is heated to a temperature between about 150 C. and 180C. for about two days, with the production of a product consistingmainly of ethers such as di-hydroxypropyl, mono-hydroxypropylaminediricinoleate ether, and more complex ethers formed by the condensationof more than two molecules or the triglycerylamine diricinoleate, etc.

"Example 11 (Example 3 of the patent) Diethanolamine monoacetate isheated to a temperature between about 150 C. and 180 C. for about twodays with the production of a anolamine, previously referred to.

product consisting mainly of the ether 01 the formula:

It is to be noted that reference is made to the above four last citedpatents in regard to a further elaboration as to various fatty acidesters, i. e., ordinary vegetable oils, fats, and the like, which may beemployed, and also as to further description of acceptable hydroxyaminesand polyhydric alcohols which may be employed. It must be recognizedthat the materials have not lost their basicity to any great degree, ascompared with the hydroxyamines from which they were originally derived.Esterification or acylation may tend to reduce the basicity to somedegree, although in some instances it may even be increased. Suchmoderate changes are immaterial.

Generally speaking, it is our preference to obtain the intermediatereactants from amines in which there is no hydrogen atom attached to theamino nitrogen atom. In other words, our preference is to use tertiaryamines, such as ethyl diethanolamine, diethyl ethanolamine.triethanolamine, etc. Generally speaking, it is our preferenceto preparethe intermediate reactants from the tertiary amines, in which there isan alkanolamine' radical present, particularly an ethanolamine radicalpresent. Furthermore, it is our preference to emplo derivatives ofglycerol in forming the ether type compound. Particular attention isdirected to the types of compounds as prepared according to thedirections in the various patents previously referred to. Incidentally,we desire to point out that T, previously referred to, may represent anRCO radical directly attached to the amino nitrogen radical. In otherwords, the intermediate reactant may also be an amide. The RCO in suchinstances may be derived from an acid having less than 8 carbon atoms,or from a detergent-forming acid. However, in such instances thebasicity of the amino radical will usually disappear in conversion intoan amide; and therefore, in such instances, it is usually necessary tohave another amino nitrogen atom present which supplies the basicity ofthe molecule. Such situation is entirely analogous to the presence of anamino nitrogen atom attached to an aryl radical, as in the case ofphenyl dieth- There is no objection to any non-basic nitrogen atomcontributing part of the molecular weight in the form of an arylamineradical, or in the form of an amide radical, provided that the compoundstill is basic, due to the presence of some other basic amino nitrogenradical of the kind previously described.

Attention is again directed to the fact that. although the precedingeleven examples are concerned largely with derivatives of unmodifiedfatty acids, yet the same procedure is also applicable to modified fattyacid compounds manufactured in the manner previously indicated, to wit,so that such modifications are still convertible into soap or soap-likebodies by agency of suitable alkalies. Similarly, one can preparecompounds of abietic acid, naphthenic acid, or modified forms thereof.It is not necessary to prepare the acylated amino-ethers from esters;but if such procedure is desired, then one can first prepare esters fromnaphthenic acid, abietic acid, or the like, which correspond tonaturallyoccurring esters; for instance, one can prepare naphthenin,abietin, or the like. We particularly prefer to prepare compoundscharacterized by the maleate. The reaction may be shown more simply asif involving the acid instead of the anhydride, thus:

presence of at least one, and preferably more than one, hydroxyhydrocarbon group in the final product. Reference is made to the factthat the table appearing in the early part of this applicationdescribing a series of representative hydroxy aminoethers, containscertain species in which the ether linkage involved combination with amonohydric alcohol. Such alcohols can vary from methyl throughoctadecyl, or stearyl, and may be normal or branched. In view of thisfact, it must be appreciated that the scope of the compoundscontemplated as intermediate reactants in the present application, maybe derived from hydroxyamines and monohydric alcohols, as well ashydroxyamines and dihydric alcohols, r from intermolecular reactions oftwo or more moles of hydroxyamines. As to the manufacture of such alkylethers of hydroxyalkylamines, it is to be noted that they can bemanufactured by means of conventional methods now employed, or bymethods which involve modification of previously described methods; orthey may be manufactured by the method described in French Patent No.

832,288, dated September 23, 1938, to Zschimmer & Schwarz,ChemischeFabrik Diilau.

Having obtained such alkyl ethers of hydroxy alkylamines by the methodsuggested in said aforementioned French Patent No. 832,288, or by anyother means, one then acylates such products in the same mannerpreviously described. As has been pointed out previously, our preferenceis to use fatty acids, particularly the fatty acid compounds, such asesters, because they are readily available in the form ofnaturally-occurring oils and fats. Among the various desirableglycerides are: Castor oil, olive oil, cottonseed oil, rapeseed oil,fish oil, menhaden oil, corn oil, cocoanut oil, palm oil, palm kerneloil, linseed oil, sunflowerseed oil, teaseed oil, neats-foot oil, etc.Our preference is that the monomeric chemical compound, exclusive ofacyl radicals, shall contain less than GOcarbon atoms, and in mostinstances, shall contain less than 25 carbon atoms. The acylatedamino-ethers used in this invention are either monoor polyaminobodies, 1. e., they contain one or more amino nitrogen atoms. In

GLYCOLESTER INTERMEDIATE PRoDUcT Example 1 One pound mole ofnonaethylene glycol is reacted with two pound moles of maleic anhydride,so as to form nonaethylene glycol dihy r s n GLYCOL ESTER INTERMEDIATEPRODUCT Example 2 A mixture of lower non-distillable polyethyleneglycols, representing approximately decato tetradecaethylene glycol, issubstituted for nonaethylene glycol in the preceding example.

GLYCOL EsTER INTERMEDIATE PRODUCT Example 3 A 50-50 mixture ofnonaethylene glycol and lower non-distillable polyethylene glycols ofthe kind described in the previous example is substi- I tuted fornonaethylene glycol in Example 1.

GLYCOL EsTER INTERMEDIATE PRoDUcT Example 4 Adipic acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

GLYcoI. ESTER INTERMEDIATE PRoDucT Example 5 Oxalic acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

GLYCOL ESTER INTERMEDIATE PRoDuc-r Example 6 Citric acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

hydride in Examples 1-3, preceding.

The method of producing such fractional esters is well known. Thegeneral procedure is to employ a temperature above the boiling point ofwater and below the pyrolytic point of the reactants. The products aremixed and stirred constantly during the heating and esterification step.If desired, an inert gas, such as dried nitrogen, or dried carbondioxide, may be passed through the mixture. Sometimes it is desirable toadd an esterification catalyst, such as sulfuric acid, benzene sulfonicacid, or the like. This is the same general procedure as employed in themanufacture of ethylene glycol dihydrogen diphthalate. See U. S. PatentNo. 2,075,107, dated March 30, 1937, to Frasier.

Sometimes esterification is conducted most readily in the presence of aninert solvent, that carries away the water of esteriflcation which maybe formed, although, as is readily appreciated, such water ofesterification is absent when the reaction involves an acid anhydride,such as maleic anhydride, and a glycol. However, ii water is formed, forinstance, when citric acid is employed, then a solvent such as xylenemay be.

present and employed to carry ofi the' water formed. The mixture ofxylene vapors and water vapors can be condensed so that the water isseparated. The xylene is then returned to the reaction vessel forfurther circulation. This is a conventional and well known procedure andrequires no further elaboration.

ascaaco 9 Courosrrron or Mama Coxrosrrron or Mama One pound mole of atertiary ether amine of the following composition: An amine of thefollowing composition:

OHCsH4 H OH H CaHAOH obtainable by the action of ethylene oxide-on tri-F ethanolamine, is reacted with one pound mole of 011cm, n H H canonricinoleic acid, so as to obtain the ester of the is employed i the amemanner as described in following compositi the preceding examples.

(CIHJOCIHAOEDI Comrosrrron or MAM-rm cmmcmmocn l5 Example 6 in which RC0is the ricinoleyl radical. In its Soyabean fatty acids are substitutedfor ricinsimplest aspect the aforementioned reaction may oleic acid inComposition of matter, Examples be indicated in the following manner:1-5, preceding.

gringoc.c,n,ooccmwmocHa-cmooc.c,n,.c oijg'ii igiocznlo CzHa cimocimo E3HOCzHiOCaH-N n clmo canon H.000C3H40C2H4 C:H4OCIH4OOC.R

Two pound moles of the ester of the composi- Courosrrron or MATTER tionimmediately preceding are reacted with one pound mole of a glycol esterintermediate prodxamp 7 not of the kind described under Glycol esterintel-mediate products, Examples 1, 2 and 3, preced- Glycol esterintermediate products of the kmd ing. Such reaction is continued untilall carexemplified by Examples precedingare boxy; acidity hasdisappeared The time of stituted for Glycol intermediate products,Examaction may vary from a few hours to as many as 9195 2 and 3,111 thePreceding six examples- 20 hours. It is to be noted that this secondstep is an es- COMPOSITION OF MATTER terification reaction, and the sameprocedure is employed, as suggested above, in the preparation Emmple zof the intermediate product. Needless to say, any

particular method may be used to produce the de- One pound mole ofhydroxyethyl ethylen disired compounds of the kind indicated. In someamine, is reacted with approximately5 or 6 pound t nces it y e desirableto conduct the moles of ethylene oxide to give a diamino typehyesterification reaction in the presence of a nondroxylated compound.Such compound is revol il in rt olvent. which simply acts as a dilactedwith ricinoleic acid and then with the glye t s s y ed ce col esterintermediate product in the same man- In the preceding examples,attention has been ner as described in Example 1, preceding. directedprimarily to the monomeric form, or at least, to the form in which thebifunctional alco- Comrosrrrox or Mar-ran hol, i. e., a glycol, and thepolyfunctional acid,

usually a bifunctional compound, react t give a Ex le 3 5 chain typecompound, in which the adjacent acid and glycol nucleus occur as astructural unit.

An amine of the following commsmon: For instance, in the monomeric formthis may be oncm. canon indicated in the following manner:

NCQH4OCH4N acid glycol acid OH 0211, c-imon If, however, one prepared anintermediate prodobtained by the etherization of triethanolamine uctemploying the ratio of three moles of maleic or the treatment of twomoles of diethanolamine anhydride and two moles of nonaethylene glycol'with one mole of dichloroethyl ether, is reacted the tendency wu1d be toproduce a product which in the same manner as described in Compositionmight be indicated in the following manner:

of matter, Example 1, preceding, with ricinoleic acid glycol e acidglycol acid acid, and then with the glycol'ester intermediate Similarly,three moles of the glycol and four product. moles of the acid might tendto give a combina- ComrosIrIoN r MATTER tion which may be indicatedthus:

Example 4 acid glycol acid glycol acid glycol acid Another way ofstating the matter is that the An amine of the following composition:composition may be indicated in the following on manner: czmoTOOC.D.COO[(C:H|O)n-1OZH|O0 C.D.C00].T BFCIHOH OH in which thecharacters have their previous sig- C H OH niflcance and :c is arelatively small whole number less than 10, and probably less than 5;and in is employed in the same manner as described in the monomeric format, of course, is 1. The limithe preceding examples. taflons on the sizeof a: are probably influenced ther growth is dependent upon randomcontact. Some of the products are self-emulsifiable oils ofself-emulsifiable compounds; whereas, others give cloudy solutions orsols; and the most desirable type is characterized by giving a clearsolution in water, and usually in the presence of soluble calcium ormagnesium salts, and frequently, in the presence of significant amountsof either acids or alkalies.

Water solubility can be enhanced in a number of ways which have beensuggested by previous manufacturing directions, for instance:

(a) By using a more highly polymerized ethylene glycol;

(12) By using a polymeric form instead of a monomeric form in regard tothe unit which forms the chain between the two alcoholic nuclei;

By using a polybasic carboxy acid of lower molecular weight, forinstance, maleic acid instead of adipic acid;

(d) By using an alcoholic ether amine of a lower molecular weight, orone having more ethereal linkages of more hydroxyl groups, or more basicamino nitrogen atoms.

Indeed, in many instances, the acylated ether amino compound is'water-soluble prior to reaction with the glycol ester. It is to benotedthat in this instance one is not limited to hydroxylated materialswhich are water-insoluble prior to reaction with a glycol ester; butthey may, in fact, be perfectly water-soluble.

Actually, a reaction involving an alcohol and an acid (esteriflcation)may permit small amounts of either one or both of the reactants,depending upon the predetermined proportion, to remain in an unreacted.state. In the actual preparation of compositions of the kind hereincontemplated, any residual acidity can be. removed by any suitable base,for instance, ammonia, triethanolamine, or the like, especially. indilute solution. Naturally, precaution should be taken, so thatneutralization takes place without saponiiication or decomposition ofthe ster. In some cases, there is no objection to the presence of theacidic group. Indeed, if a tribasic acid be employed in such a manner asto leave one free carboxyl group, then it is usually desirable toneutralize such group by means of a suitable basic material.

In the hereto appended claims, reference to a neutral product refers toone in which free carboxylic radicals are absent.

Materials of the kind herein-contemplated may find uses as wetting,detergent, and leveling agents in the laundry, textile, and dyeingindustry; as wetting agents and detergents in the acid washing of fruit,in the acid washing of building stone and brick; as a wetting agent andspreader in the application of asphalt in road buildin and the like, asa constituent of soldering flux preparations; as a flotation reagent inthe flotation separation of various minerals; for flocculation andcoagulation of various aqueous suspensions containing negatively chargedparticles such as sewage, coal washing waste water, and various tradewastes and the like; as germicides, insecticides, emulsifiers forcosmetics, spray oils, waterrepellent textile finish, etc. These usesare by no means exhaustive.

However, the most important phase of the present invention, as far asindustrial application goes, is concerned with the use of the materialspreviously described as demulsiflers for water-inaseaaso' oil emulsions,and more specifically, emulsions of water or brine in crude petroleum.

A somewhat analogous use of our demulsifying agent is the removal of aresidual mud sheath.

which remains after drilling by the rotary method. Sometimes thedrilling mud contains added calcium carbonate or the like t render themud susceptible to reaction with hydrochloric acid or V the like, andthus expedite its removal.

Chemical compounds of the kind herein described are also of value assurface tension de-.

pressants in the acidization of calcareous oil- .bearing strata by meansof strong mineral acid. such ashydrochloric acid. Similarly, somemembers are effective as surface tension depressants or wetting agentsin the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agentsfor recovering oil from subterranean strata, reference is made to theprothat residual carboxyl acidity can be eliminated.

by esterification with a low molal alcohol, for instance, ethyl, methyl,or propyl alcohol, by con-. ventional procedure, so as to give asubstantially neutral product. The introduction of such low molalhydrophobe groups does not seriously afiect the solubility, and in someinstances, gives increased resistance, to soluble calcium and magnesiumsalts, for such property is of particular value. Usually, however,neutralization with a dilute solution of ammonia or the like is just aspracticable and less expensive,

In the hereto appended claims, it is intended that the monomeric formscontemplate also the polymeric forms, insofar that the polymeric formsare nothing more or less than a repetition of the monomeric formsseveral times over, with the loss of one or more moles of water. Thesimplest compound herein contemplated is the octanoic acid ester of thefollowing previously illustrated amine:

N-CzHrOH 0:11.011

Such, ester, which is illustrated by the following formula:

has a molecular weight of 301. On the other hand, as previously pointedout, hydroxyaminw ethers having a plurality of hydroxyl groups may bereacted with acids having as many as 32 carbon atoms, and thus theuppermolecular weight range may be approximately 3,000 or higher. As hasbeen emphasized, the products are basic in nature, 1. e., contain abasic amino nitrogen atom. Reference to a basic amino nitrogen atom isused in its conventional sense. Unsaturated groups, or negative groups,if substituted for one or more of the hydrogens or ammonia, reduce thebasicity of the nitrogen atom to a remarkable degree. In

general, the presence of one negative group linked on the nitrogen issumcient to destroy the ordinary basic properties. (Textbook of OrganicChemistry, Richter, 2nd edition, page 253.)

Re-examination of the prior formulas showing the composition of thehydroxylated acylated basic aminoethers indicates there may be presentat least four alcoholic hydroxyl radicals available for esterificationwith nonaethyleneglycol dihydrogen dimaleate, or the like. Thus,momentarily, it is more convenient to consider such hydroxylatedcompound as an alcohol, thus:

R5(0H) w wherein R5 is the hydroxylated acylated basic aminoetheralcohol residue and m represents a small whole number varying from 1 to4.

The hydroxylated, acylated aminoether radical R5 having at least oneoccurrence of the radical in which RsCO is the acyl radical of amonocarboxy detergent-forming acid having at least 8 and not more than32 carbon atoms; the amino nitrogen atom is basic; R2 is a. polyalkyleneradical or its equivalent, such as hydroxy polyalkylene in which thealkylene radical have at least 2 and not over 10 carbon atoms, and n isa small whole number varying from 1 to 10, the molecular weight of saidcompound in monomeric form being from in excess of 300 to approximatelytenfold such value, and the basic hydroxy aminoether radical unattachedto the acyl radical containing not over 60 carbon atoms.

What has just been said can be recapitulated and presented in moreformal agreement with customary nomenclature in the following manner: Asstated previously, in the broadest aspect, the polyalkylene glycolsemployed may be indicated by the following formula:

OH (CnHZnO) mH in which m has its previous significance, and nrepresents a numeral varying from 2 to 4, and m varies from '7 to 1'7.In simpler form this structure can be indicated in the following manner:

in which the divalent radical R0 is the divalent radical (CnH2nO)m, aspreviously defined.

The dibasic acid previously referred to, in its simplest form asHOOC.D.COOH is more completely portrayed by the following formula:

coon

RFCOOH 00011). in which R1 is the polybasic carboxy acid residue, exceptin the unique case of oxalic acid, and q is the numeral 0 or 1,depending on whether or not the polybasic acid is dibasic or tribasic.

If the polybasic acid just described is indicated by R, and if theglycol just described is indicated by R", then the acidic or fractionalester previously described earlier in the specification may be indicatedby the following formula:

in which p and p represent numerals varying from 1 to 10, and nrepresents a numeral varying from 1 to 20, and R and B." have theirprior significance, and the ratio oi. p to p varies from 2:1 to p+1:p',with the obvious proviso that such ester must contain at least two freecarboxyl radicals.

The new composition of matter herein contemplated is best represented asan ester obtained by the esterification reaction involving the acidicfractional ester above described and the hydroxylated acylated basicaminoetheralcohol previously depicted in detail. The final compositionmay be obtained in any suitable manner and would properly represent thefinal product, regardless of the succession of the intermediate steps.So portrayed, the structural formula is as follows:

in which all of the characters have their prior significance, and nrepresents a numeral varying from 1 to 4, and n represents a numeralvarying from 1 to 4, and n"" represents a numeral varying from 1 to 4.

It has previously been pointed out in the specification that anyresidual carboxylic radicals, and especially one obtained from tribasicacids, could be neutralized with a variety of suitable basic materials.In other words, a residual carboxylic hydrogen atom may be replaced by ametallic atom, an ammonium radical, or substituted ammonium radical, aspreviously indicated. Under such circumstances, any residual carboxylicradical, instead of appearing thus: COOH. may, in essence, be theradical COORe in wh ch Re represents a cation including the acidichydrogen atom. This can be best disposed of by rewriting the formula forthe polybasic carboxy acid, thus:

' coon Iii-coon 000m), in which all of the characters have their priorsignificance.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. A water-soluble ester of the formula:

[a mil -'1e1 llll in which n" represents a numeral varying from 1 to 4,n' represents a numeral varying from 1 to 4, and 11"" represents anumeral varying from 1 to 4, and in which 9 and p represent numeralsvarying from 1 to 10, and the ratio of p to p varies from 2: 1 to p+l:p, and p" represents a numeral varying from 1 to 20, and R is a glycolof the formula HO-R OH in which the divalent radical RO- is the divalentradical (CnH21|.0) m in which radical, in turn 11. represents a numeralvarying from 2 to 4 and m represents a numeral varying from 7 to 17; R"is the polycarboxy acid coon iii-coon in which R1 is the polycarboxyacid residue, and R1 is a cation, and q is the numeral 0 or 1:

is a hydroxylated acylated basic aminoether alcohol in which R is ahydroxylated acylated basic aminoether alcohol residue, and m representsa small whole number varying from 1 to 4; the hydroxylated acylatedaminoether radical Rs having at least one occurrence of the radicalRaCO.(ORz)n'N in which R3 is the acyl radical 'of a monocarboxydetergent-forming acid having at least 8 and not more than 32 carbonatoms; the amino-nitrogen atom is basic; R2 is a polyalkylene radical inwhich the alkylene residue has at least 2 and not over 10 carbon atoms,and n is a small whole number varying from 1 to 10; and the basichydroxyaminoether radical calculated as unattached to the acyl radicalcontaining not over 60 carbon atoms.

2. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0.

3. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, and n represents the numeral 2.

4. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, and m represents a numeralvarying from '7 to 11.

5. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, m represents a .numeral varyingfrom 7 to 11, and Rico is an 18 carbon atom fatty acid residue.

6. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, m represents a numeral varyingfrom '7 to 11, R400 is an 18 carbon atom fatty acid residue, and theratio of p to p is 2 to 1.

7. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, m represents a numeral varyingfrom 7 to 11, R400 is an 18 carbon atom fatty acid residue, the ratio ofp to p is 2 to 1, and with added neutralization of all residual acidity.

8. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, m represents a numeral varyingfrom '7 to 11, RACO is a ricinoleic acid residue, the ratio of p to p is2 to 1, and with added neutralization of all residual acidity.

9. A water-soluble ester, as defined in claim 1, wherein all occurrencesof q are 0, n represents the numeral 2, m represents a numeral varyingfrom '7 to 11, RACO is a ricinoleic acid residue, the ratio of p to p is2 to 1, with added neutralization of all residual acidity, and R1 is anadipic acid residue.

10. A water-soluble ester, as defined in claim 1, wherein alloccurrences of q are 0, n represents the numeral 2, 111. represents anumeral varying from 7 to 11, R400 is a ricinoleic acid residue, theratio of p to p is 2 to 1, with added neutralization of all residualacidity and R4 is a succinic acid residue.

11. A water-soluble ester, as defined in claim 1, wherein alloccurrences of q are 0, n represents the numeral 2, m represents anumeral varying from 7 to 11, R400 is a ricinoleic acid residue, theratio of 1) to p is 2 to 1, with added neutralization of all residualacidity and R is a maleic acid residue.

12. In the manufacture of the esterification product described in claim1, the steps of: (A) esterifying a polyalkylene glycol having at least 7and not more than 17 ether linkages; and the alkylene radical thereofcontaining at least 2 and not more than 6 carbon atoms, with a polybaslc.carboxy acid having not more than 6 carbon atoms in the predeterminedratio 01. more than 1, and not more than 2 moles of the polybasic acidfor each mole of the glycol, to produce a watersoluble product; (B)esteritying one molal proportion of said alkylene glycol dihydrogen acidester with 2 moles of a hydroxylated acylated amino ether containing:(a) a radical derived from a basic hydroxyaminoether, and said radicalcontaining at least one amino nitrogen free from attached aryl andamido-linked acyl rad--v icals; said hydroxyaminoether radical beingfurther characterized by the presence of at least one radical derived,from a basic hydroxyamine and being attached by at least one ether linkae to at least one radical selected from the class consisting of glycerolradicals, polyglycerol radicals, glycol radicals, polyglycol radicals,basic hydroxyamine radicals, amido hydroxyamine radicals, and arylalkanolamine radicals; said basic hydroxyaminoether radical beingcharacterized by containing not over carbon atoms; and (b) an acylradical derived from a detergent-forming monocarboxy acid having atleast 8 carbon atoms and not more than 32 carbon atoms, said acylatedaminoether being additionally characterized by the fact that saidaforementioned acyl radical is a substituent for a hydrogen atom of analcoholic hydroxyl radical.

MELVIN DE GROOTE. BERNHARD IGIISER.

